| With the swift progress and develop of the medicine industry in recent years, medicine industry rise year by year in specific gravity in national economy. However, pharmacy waste water also becomes main pollution sources to many water bodies, which was a hotspot problem of the environment protection field. Cause of the shifty water quality, large flow, and great amount and species of the non-biodegradable organic in it, the Pharmacy waste water could not be treated by ordinary sewage treatment technology solely. The high thickness and non-biodegradable pharmacy waste water is the investigate subject in this study, started with to promote water biodegradability, the pharmacy waste water combined treatment handicraft has been investigated, and has got fairly good effect. The treated outflow quality from this processes can accord with the national discharge standard(GB 8978-1996).According to the peculiar characteristic of pharmacy waste water and metal polyoxometalates, with the stencil of natural material (filter paper), a new stype nanoscale metal polyoxometalates catalyst, Zn1.5PW12O40 nanotubes, had been designed and composed autonomously during this study, which adopted the sol and gel method. Zn1.5PW12O40 nanotubes has good water resistance and easy to be separated from water. A routine represent method for polyoxometalates has been adopted to the Zn1.5PW12O40 nanotubes. Observed by transmission electron microscope, the crystal grain conformation is hollow nanotubes, tubes length between 200-900nm, the tubes diameter is 70 nm, the hollow tubes inside diameter is 20 nm about. Adopted the element analysis approach, the Zn1.5PW12O40 nanotubes catalyst compositions has been confirmed. The study result was that: Zn1.5PW12O40 nanotubes polyanion still maintain the initial Keggin type structure, in which Infrared Spectrum and X-ray powder diffraction (XRD) and 31P magnetic resonance (31P MAS NMR) methods had been used.Through the common use method in the world, the Zn1.5PW12O40 nanotubes has been evaluated, which was used to evaluate the catalysis activity of polyoxometalates at present.In the study Safranine T was taken as the characteristic material, which has the similar constructure to Rhodamine B, but more difficult to be biodegraded. The catalysis activity of Zn1.5PW12O40 nanotubes has been investigated by degraded the Safranine T, included photocatalysis activity and chemistry catalyzing the result indicated that: Zn1.5PW12O40 nanotubes catalysis activity is fair good.In three catalytic oxidation systems, which include ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system, Zn1.5PW12O40 nanotubes catalysis effect to non-biodegradable pharmacy waste water had been studied systematically. Only in the USA and Japan etc., polyoxometalates (POM) was applied in photocatalysis chemistry field now, and the studying were mainly carried on the purely-organics, the practical apply study is still few.The optimum operate condition of Zn1.5PW12O40 nanotubes catalyzes oxidation for the pharmacy waste water in ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system has been got in this research. The particular results as follow:(1)Takes the promotion of bio-degradability and remove rate of COD as the index, the optimum operation condition of Zn1.5PW12O40 nanotubes catalyzing oxidation treats the non-biodegradable pharmacy waste water under room temperature and pressure air system has been obtained. The results is that: air flow rate is 4.5L/h, and temperature is 50℃, and initial pH is above 9, and catalyst amounts is 30g/L, and reaction time 24 hours. There are three influent factors within above, which are air flow rate and catalyst amount and reaction time, which took the remarkable effect to the experiment results. Under the optimum operation condition, the B/C of pharmacy waste water can be promoted from 0.05 to 0.3, which can be propitious to follow bio-process.(2)The experiment of Zn1.5PW12O40 nanotubes/ O3 Catalyzes Oxidation treated non-biodegradable pharmacy waste water has been carried out, the results indicated that: Zn1.5PW12O40 nanotubes catalyst have the very good adsorption and high surface activity. It was able to accelerate ozone decomposition generating the Hydroxyl Radical·OH, that makes the difficult to degrade organic by ozone (for instance nitrobenzene and pyrrolidinone etc.) can be degraded under O3/Zn1.5PW12O40 handicraft process, at the same time, can shorten the reaction residence time, and accelerate oxide reaction speed, cut down the sources of energy consumption and treatment cost. With this process, the B/C of pharmacy waste water can be promoted from 0.05 to 0.6, which can be propitious to follow bio-process. The obtained optimum operation condition of O3/Zn1.5PW12O40 nanotubes is that: catalyst amounts is 2g/L, and Ozone liquid phase thickness is above 0.3mg/L, initial pH between 7.59, reaction time is more than 10 minutes. Within those influent factors, the reaction time and ozone thickness made the great effect to the experiment results. On the COD remove rate, it was 46% when ozone thickness was 0.1mg/L, but it can reach 85% when ozone thickness was 0.3mg/L.By way of comparison and analyses the economy and maneuverability of O3/Zn1.5PW12O40 nanotubes catalytic oxidation system and air oxidation system and ultraviolet radiation system, the practical pretreatment process was confirmed to be O3/Zn1.5PW12O40 nanotubes catalytic oxidation system. This system can promote the bio-degradability of waste water, and can make the COD remove rate above 74% at the same time.The mechanism of Zn1.5PW12O40 ultraviolet radiation degrade phenol and O3/Zn1.5PW12O40 nanotubes catalytic oxidation degrade aniline has been studied on. Through detect the intermediate product by way of GC/MS to conclude the mechanism of Zn1.5PW12O40 ultraviolet radiation degrade phenol and O3/Zn1.5PW12O40 nanotubes catalytic oxidation degrade aniline:·OH free radical plays the leading role, and a series of chemical reaction has carried out effective degradation on complicated organic from free radical initiation.Using GC/MS, the inflow and outflow waste water component from the O3/Zn1.5PW12O40 nanotubes catalytic oxidation system have been mensurated and analyzed. Result indicates: under a certain process condition, the 44 kinds organic in the raw waste water, include some non-biodegradable organic such as nitrobenzene and aniline and pyridine and pyrimidine, transformed to alcohol and carboxylic acids and aldehyde and ester and alkane after treated by O3/Zn1.5PW12O40 system. Bio-toxicity of Waste water reduces obviously, but the bio-degradability improves obviously.Adopt UNITANK-BAF combined process treat the waste water, which treated by Zn1.5PW12O40/ Ozone Catalyzes Oxidation, and had obtained the optimum operation condition. This process can reduced the raw waste water COD thickness from 40005000mg/L to 500mg/L below. The obtained optimum operation condition of UNITANK-BAF combined process treat the out flow waste water from Zn1.5PW12O40/Ozone Catalyzes Oxidation as follow:○1 UNITANK: sludge thickness is 50006000mg/L, and DO 24 mg/L, and ratio of gas and liquid is above 100:1, and inflow COD thickness 40005000mg/L, BOD 24003000mg/L, pH is 6, and BOD:N: P=100: 5:1,and HRT is more than 60 hours, room temperature 2030℃.○2 BAF: pH 6-7, ratio of gas and liquid is above 15:1, and HRT is more than 6 hours, and room temperature 2030℃. Under this operation condition, the average COD remove rate of UNITANK-BAF combined process can reach 91.4%.The out flow is limpidity and lucent, COD thickness lower than 500 mg/L, accord with the national waste water discharge standard. Prove that: That Zn1.5PW12O40/ Ozone Catalyzes Oxidation is an effective pretreatment process to the high concentration non-biodegradable pharmacy waste water. Zn1.5PW12O40/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process is the suitable handicraft for the high concentration non-biodegradable pharmacy waste water.Non-biodegradable pharmacy waste water treated by Zn1.5PW12O40/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process had been detected with GC/MS, results indicated: after treated by Zn1.5PW12O40/O3 Catalyzes Oxidation-UNITANK-BAF allying unite process, the organic detected in Non-biodegradable pharmacy waste water out flow were small molecule carboxylic acid and alcohol, bio-toxity was less, and the out flow is limpidity and lucent, COD thickness was below 500mg/L, which can accord with the national discharge standard(GB 8978-1996). This study a new style catalyst, Zn1.5PW12O40 ultraviolet, has been achieved to exploited. Used with ozone Oxidation, this catalyst can promoted the sewage biodegradability observably, and then the non-biodegradable pharmacy waste water treated continually by UNITANK-BAF combined process can accord with the national discharge standard(GB 8978-1996). The results have important theory meaning and guide function, as well as significance applying value, to the waste water contain non-biodegradable organics.
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